System for combustion of fuel to provide high efficiency, low pollution energy

ABSTRACT

An afterburner system and method for reducing the CO2 and other pollutants produced by the combustion of a fuel in a combustion chamber while maintaining or increasing the efficiency of said combustion includes feeding a catalyst, preferably lithium and/or boron to the afterburner, or a preconditioning afterburner, along with the exhaust from the combustion chamber. The presence of the catalyst in the after burner results in further reduction of pollutants generated by the combustion in the combustion chamber.

This application is a Continuation-in-Part of Ser. No. 15/633,664 filedJun. 26, 2017, now U.S. Pat. No. 10,082,288 issued Sep. 25, 2018, whichis a Divisional of U.S. application Ser. No. 13/175,761 filed Jul. 1,2011, now U.S. Pat. No. 9,702,546, issued Jul. 11, 2017, which is aDivisional of U.S. application Ser. No. 12/914,921 filed Oct. 28, 2010claiming benefit of U.S. Provisional Application 61/361,323 filed Jul.2, 2010.

FIELD OF THE INVENTION

Processes utilizing catalysts to reduce carbon dioxide and other harmfulemissions from fossil fuel combustion which increase heat and energyproduction, improve efficiencies of engines, boilers and turbines andincrease oxygen in the exhaust streams from fossil fuel combustionprocesses are described.

While the invention described herein is applicable to all fuel burningdevices including, but not limited to, burners, combustion chambers andengines, in a particular embodiment an engine with reduced carbon oxideemissions is conditioned by the presence of a catalyst, such as lithium,during the combustion process of hydrocarbon fuel containing lithiumresulting in continued reduced carbon oxide emissions during thecombustion process of hydrocarbon fuel when compared with the sameengine operated without the catalyst addition. The process andprocedures set forth herein also relate to a method of combusting ahydrocarbon fuel in a hydrocarbon powered engine having an internalsurface conditioned by combusting a hydrocarbon fuel containing thecatalyst (e.g., a lithium salt to provide a lithium conditionedsurface), wherein the effluent gas has a lower concentration of carbonoxides than combusting the fuel under similar conditions in an enginenot having a lithium conditioned surface.

The additive contemplated for use in the present invention includes, ina preferred embodiment, lithium salts, specifically lithium nitrate, inorganic or aqueous solvents including isopropanol. The particularmetallic salts added to engine fuels as set forth herein have been foundby applicant to increase internal combustion engine efficiency anddecrease vehicle gaseous emissions such as CO, CO₂, C₆+, and othercompounds. These phenomena are dependent on many parameters includingthe fuel chemical composition and interaction as well as exposedphysical environment.

In a particular embodiment, the engines contemplated for use in thepresent invention include the gasoline-powered internal combustionengines ignited by spark and also compression internal combustion(diesel) engines.

BACKGROUND OF THE INVENTION

There is an urgent need to reduce the emissions of carbon dioxide (CO₂),which is a green house gas caused by the combustion of fossil fuels andis identified as the primary cause of global warming. There is also aneed to reduce many harmful pollutants identified with fossil fuel usereported to be causing serious health problems worldwide.

It is generally agreed that combustion processes are extremely complexwith many reactions and processes occurring over very short time spansmeasured in micro seconds. Our knowledge of the gas or vapor phase ofcombustion also indicates that the atoms and molecules in the gas phaseare undergoing over 10 billion violent collisions/second. Some of thescientific roots of this process have been found to be in the emergingfield of Condensed Matter Physics which is concerned with understandingdistinct states of matter, namely gas, liquid, solid, and plasma. Thediversity of systems and phenomena included in this field makescondensed matter physics the largest field of contemporary physics. Itis also reported that one third of all United States physicists identifythemselves as condensed matter physicists. According to currentliterature this field has a large overlap with chemistry, materialsscience, and nanotechnology, and there are close connections with therelated fields of atomic physics and biophysics. Theoretical condensedmatter physics also shares many important concepts and techniques withtheoretical particle and nuclear physics setting a clear precedent forthe claims of this invention.

Catalysts are commonly used to reduce pollution levels. However, thecatalysts of identified herein are not commonly used. Their higheffectiveness is attributed to a very high level of particle activationproduced by the process described herein.

Currently there is only one primary approach being seriously consideredand funded for of preventing carbon dioxide levels from continuing tobuild up in the earth's atmosphere and cause the severe climate changesidentified with global warming. The principal method being considered,namely carbon capture and storage (CCS), is a very expensive and apotentially dangerous process. Capturing and compressing CO₂ requiresthe use of a considerable amount of energy and would increase the fuelneeds of a coal-fired plant utilizing CCS by 25%-40%. These and othersystem costs are estimated to increase the cost of energy from a newpower plant with CCS by 21-91%. These estimates apply to purpose-builtplants near a storage location. Applying the CCS technology topreexisting plants or plants far from a storage location is moreexpensive. A prominent government official with responsibilities tosolve this problem has termed this challenge a nightmare. Carbon dioxideunder high pressures used in this process are quite slippery and leaksthat have occurred have been lethal to animals and humans.

Some other solutions being investigated include deep ocean storage withthe risk of greatly increasing the problem of ocean acidification, deadzones, reef destruction and sea life kill-off in a manner similar totoxic and acid laden air pollution.

Although the processes involved in CCS have been demonstrated in someisolated industrial applications, no commercial scale projects whichintegrate these processes exist, and therefore the costs are uncertain.However, some recent credible estimates indicate that a carbon price ofUS$60 per US-ton is required to make capture and storage competitive,corresponding to an increase in electricity prices of about 6 cents perkWh.

A method of growing algae as a means to capture CO₂ is being developed.However, this procedure it is still in the experimental and developmentstage. Cost and capacity are a challenge and it does not seem to bescalable to a sufficient level to turn around the current trends incarbon dioxide accumulation in the atmosphere.

The process described herein brings with it a huge financial incentivefor the profit lines of users because of reduced fuel consumption. Withthis comes less fuel throughput producing less pollution. In addition,the process also reduces pollution levels from fuels burned.

As oil dependence increases, proven reserves become depleted and sourcessuch as strategic reserves enter into fall-back planning, the processset forth can become a strategic reserve in its own right and a viablesolution to the issue of oil depletion and dependency on unfriendly andunstable suppliers to a civilization vitally dependent on energy,especially foreign oil supplies with exposure to vulnerable “choke”points in worldwide supply systems.

Coal is also being recognized as a major source of contamination and hasbeen universally recognized as a “dirty” energy source. This process setforth herein brings the promise of clean coal and a revitalized economyfor the world with rising employment statistics.

SUMMARY

Set forth herein is a method for utilizing catalysts to reduce carbondioxide and other harmful emissions generally produced in fossil fuelcombustion processes. The method is directed to a controlled processwhich reduces CO₂ and other air pollution levels and increases thermalefficiency. The method includes a process for controlling, regulatingand optimizing the complex interactions in gas and plasma states offossil fuel combustion. The methods and processes disclosed herein areunique and unobvious methods of optimizing the use of catalysis infossil fuel combustion processes, providing for the initiating andcontrolling or regulating a process which results in reduced CO₂ andother air pollution levels and increased thermal efficiency. As aresult, CO₂ and other harmful air pollutants are significantly reducedwhile thermal efficiencies are brought to new higher levels. Theoptimizing steps include not only positive methods but also steps toelimination moderators that work against the effectiveness of theprocesses. One aspect of these processes are interactions with chambersurface components such as boiler tube walls, cylinder confines,insulation materials exposed to combustion and the combustion gases. Asa result of these controlled methods of operation, harmful airpollutants are significantly reduced while thermal efficiencies arebrought to new higher levels.

One aspect of the process set forth herein is to provide a method forreducing CO₂ at its source in fossil fuel combustion processes which issimple, inexpensive and can be applied worldwide in a short period oftime without need for complex and expensive mechanical operations andequipment such as scrubbers, precipitators, bag houses, particulatetraps and fly ash collectors, catalytic converters and complex controlsystems that have emerged as solutions to combustion pollution problemssince the 1970's. Furthermore, the process reduces energy expenses forall users of coal, oil and gas including electrical generation. Stillfurther, the process is useful for combating the specter of globalwarming and reducing the tremendous harm being caused by air pollutionto humans, the environment, to other life forms and forests whileproviding cheaper energy as an incentive to invest in this technologyfor the common good. Further, the process increases profits and lowersenergy bills while reducing harmful pollution, especially CO₂ suspectedto be a cause or global warming. Still further, while the process isreducing CO₂ it also produces oxygen which is a further beneficialresult.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the results of a series of tests in a furnace.

FIG. 2 shows results of the process in automotive tests using FederalTest Procedure protocol.

FIG. 3 shows results of a CO₂ test series.

FIG. 4 shows Carbon dioxide reductions using a lithium catalyst.

FIG. 5 is a graph showing carbon dioxide reductions using a lithiumcatalyst in a two batch burn off of high carbon briquettes.

FIG. 6 is a graph showing the benefit of using a potassium activator toproduces a greater CO₂ reduction in batch type carbon burn off.

FIG. 7 shows the effect of combustor wall area on CO₂ reduction usingthe process incorporating features of the invention.

FIG. 8 shows the effect of combustor wall roughness on carbon dioxidereduction.

FIG. 9 is a copy of the Dry Flue Gas Combustion Chart published byBabcock & Wilcox in the book, Steam Generation and Use.

FIG. 10 is a graph showing the CO₂ reductions produced in a furnaceburning anthracite coal.

FIG. 11 is a graph showing over 300 boiler tests with efficienciessignificantly higher than the design values for various boilers theywere run on.

FIG. 12 illustrates the before and after results from a boiler test.

FIG. 13 shows a calibration check for the accuracy and repeatability ofa test boiler comparing heat loss measurements to calorimetricmeasurements.

FIG. 14 shows the effect of addition of lithium catalyst on energyoutput in a series of 4 boiler tests.

FIG. 15 illustrates the energy spike following catalyst deliveryfollowed by a decrease of energy output.

FIG. 16 illustrates several examples of excess energy caused by thecatalyst delivery peaking and then falling off after moderatinginfluences came into play.

FIG. 17 illustrates the operation over a 1 month period of a 500,000million BTU per hour refinery boiler.

FIG. 18 illustrates an effort to return the test boiler to its originalbaseline condition. In spite of thoroughly cleaning and installing a newinsulating ceramic liner efficiency remained significantly above thebaseline datum under steady state conditions.

FIG. 19 shows a step-wise optimizing procedure used to gradually reducecarbon dioxide and pollutant emissions as well as improving efficiency.

FIG. 20 illustrates the step wise reduction of combustion air which inturn reduced the inhibiting effect of the air on the catalyzedcombustion.

FIG. 21 illustrates the capability to turn off the reaction quickly bysharply increasing the excess air at the burner.

FIGS. 22 and 23 are schematic representations of a hydrocarbon compoundbeing bombarded by activated or excited protons as a result of thepresence of the catalyst in the processes, the kinetic energy of thoseprotons shearing the hydrocarbon chains into smaller pieces.

FIG. 24 is a schematic representation of an afterburner systemincorporating features of the invention described herein.

DETAILED DESCRIPTION

It has been found by applicant that when catalysts, such as lithium andcertain other catalysts disclosed herein, are used in the combustionprocesses and are controlled at very precise concentrations, thebeneficial improvements shown in the following figures and tablesresult. Operating parameters for optimal operating, optimized reductionsof numerous emissions have been produced as a result of unique controlof the catalytic processes. Additionally, improved efficiency, reducedfuel and oxygen consumption and other beneficial results can be broughtabout and maintained despite the many challenging dynamic interactionspresent that have prevented these discoveries in the past.

Various different combustion chambers or burners are used in theprocesses for combusting the many and varied fossil fuels including, butnot limited to, gases such as propane, methane and natural gas, oilssuch as gasoline, diesel and petroleum residuals and various ranks andtypes of coals as well as biofuels. These fuels are used in manydifferent combustion chambers, such as furnaces, boilers, engines andturbines. In addition, many other types of controlled reaction chambersare suitable for producing higher levels of heat and energy with thescope of the invention described herein. Certain other designs aresuitable for after-treatment of pollution laden exhaust systemscontaining toxic and contaminated gases and affluent from chemicalprocessing and detoxification of contaminated materials such as coal ashand radioactive wastes.

In a particular embodiment, improvements to a combustion enginecomprising the use of a lithium conditioned chamber for producingreduced carbon oxide engine emissions are disclosed. Preferably, thelithium conditioned chamber is formed by combusting a hydrocarbon fuelcontaining a lithium salt in the chamber.

Described herein are methods of combusting a hydrocarbon fuel containinga lithium salt in a hydrocarbon powered engine to produce a lithiumconditioned chamber in the engine, and combusting a lithium freehydrocarbon fuel in the conditioned chamber in order to produce a lowconcentration effluent gas. The low concentration effluent gas has alower concentration of carbon oxides than an effluent gas from an enginewithout a conditioned chamber combusting the same lithium freehydrocarbon fuel.

Disclosed is a novel addition of lithium nitrate to gasoline or dieselpowered vehicles to cause internal engine conditioning or surfacealteration due to the combustion process occurring in the presence oflithium nitrate.

Also disclosed is a method of conditioning the internal combustionsurface of an engine of a gasoline or diesel-powered vehicle bycombusting a hydrocarbon fuel, including lithium nitrate, to obtain anengine capable of providing emissions having a lower concentration ofcarbon oxides than obtained by combusting the same hydrocarbon fuelunder similar conditions in an engine not having lithium conditionedsurface.

Also provided is a method of conditioning the internal surface of adiesel powered vehicle by combusting a hydrocarbon fuel, includinglithium nitrate, to obtain an engine capable of providing loweremissions, namely lower concentrations of carbon oxides and a lowerconcentration of hydrocarbons than obtained by combusting a hydrocarbonfuel under similar conditions in an engine not having a lithiumconditioned surface.

The present process also provides a method of conditioning the chambersof an internal combustion gasoline or diesel engine of a vehicle bycombusting a hydrocarbon fuel, including lithium nitrate, to obtain anengine capable of providing an emission gas having a lower concentrationof carbon oxides than obtained by combusting a hydrocarbon fuel undersimilar conditions in an engine not having a lithium conditioned enginechamber.

A method of combusting a hydrocarbon fuel in the presence of a lithiumsalt is disclosed to obtain a vehicle engine effluent having reducedcarbon oxide emissions.

The method of combusting hydrocarbon fuels containing a lithium saltprovides a lithium conditioned engine surface, wherein the effluentemission gas contains a lower concentration of carbon oxides and a lowerconcentration of C₆+ alkanes than combusting said fuel under similarconditions in an engine not having a lithium conditioned surface.

Depending on the desired results, different operating conditions areestablished using an array of instruments, sensors, transmitters,computer and software interface, algorithms for specific end objectives,transmission links and all the various components for the myriad ofapplications possible which have been developed for the art of plantmanagement and control.

One aspect of the process is that it usually requires a mass of catalystless than about one millionth of the mass of the combustion productstreated.

In a preferred embodiment, a gaseous state is created and utilized incommonly available combustion chambers to produce desired catalyticreactions. Specifically, the chamber must be hot enough to evaporate anddiffuse the catalyst and other constituents into a gaseous state so asto cause atoms and molecules in the combustion chamber to collide andinteract at a very high rate, preferably over a billion times a second.When sufficiently initiated, the intense particle activity createdproduces numerous desired effects.

The combustion chamber can be any size or shape, but should be strongenough to withstand high pressures or vacuums required for specificcombinations of catalysts and processes. Reaction chambers can alsorequire high temperature insulation to maintain operating temperaturesand to protect the metal surfaces from overheating. Operatingtemperatures of chambers must be sufficiently high to maintain contentsin a vapor or plasma state. Ordinary combustion chambers such asfurnaces, boilers, engine cylinders, and gas turbine combustors are someexamples that serve this purpose in existing equipment. In light of theteachings herein, special chambers can be designed to serve manyadditional purposes. It is also contemplated that the chambers can befabricated from materials seasoned with the catalyst before constructionof the chamber. They can be opened or closed to atmosphere to generateheat and electrical power. For example, they can comprise closed or openended piping or ductwork systems such as boiler breechings and stackswhere the process can be activated and continued as other, possiblycontaminated, streams pass through the same confines for treatments.

The non-combustion system has several attractive features, namely theycan operate at pressures above atmospheric and with vacuums.Additionally, they work as non-emitting systems and they completelyutilize all introduced catalysts. Applicant has shown that coating theinside surface of the non-combustive system with a suitable catalysts(see Table 3) and activators such as potassium and thorium work well forrepeated activation cycles. However, this can also be accomplished withhigh voltage arcs and high temperature vaporizing units. As analternative means to activate the chamber, a combustion process can beused to precondition the chamber, vaporizing catalysts and activators.The combustion can then be turned off with the reaction continuing as aself-sustaining process.

An objective of the control system is to maintain an activated gaseousstate under optimum operating conditions. The catalysts, especiallylithium, are active in the combustion zone, but also have a moderatinginfluence when concentration is not maintained in a target range of 0.1to 0.5 part per million (100 to 500 parts per billion) lithium. Outsideof this range benefits of the catalyst may be diminished or turned off.Optimal control logic searches out and maintains the desired resultwhich may be found at other concentrations.

Particle activity caused by select catalysts produces extremely hightemperature events. These events cause the catalysts to become embeddedand sometimes fused or alloyed with the chamber's base materials. Inaddition, catalyst particulates condense and adhere to chamber surfacesand are embedded in microscopic crevices and inter-granular spaces ofmetals and insulation. These then serve as origin points for catalystsand the enhanced activities of this catalyzed process. This conditioningprocess is referred to as “seasoning.” It is manifest as a long terminfluence which continues, often producing significantly increased heatand energy production accompanied pollution reductions, well beyond thepoint in time when catalyst is no longer being added to the reactionzone. Furthermore, this ongoing seasoning effect continues working afterthorough cleaning of metal surfaces and replacement of insulatingmaterials. In a particular chamber, the effect could only be turned offby replacing the combustion chamber itself, after which efficienciesreturned back to the normal levels advertised by the manufacturer andmeasured during baseline testing programs prior to addition of thecatalyst.

Radiant energy transfer, occurring in flame zones, is very efficientwhen compared to convection and conduction of energy. Radiant heattransfers exponentially with the absolute temperature. Measured hightemperature events caused by the catalyst accounts in part for thehigher efficiencies and increased power produced when certain catalystsare present.

The described process is simple because it requires no significantcapital investments for immediate application in existing fossil fuelapplications. The described compositions are simply added to the fuelsupply at precise ratios. The catalysts are largely benign, non-poisons,non-heavy metals which are non-toxic and non-radioactive safeformulations. In addition, they can be shipped by common carriers withno restrictions. The value of fuel savings alone far outweighs its cost.

Reduction of carbon dioxide emissions is accomplished in two ways by thedescribed process. First, carbon dioxide is transformed into benigncompounds and elements. Secondly, the amount of fossil fuel consumed isreduced with new high levels of efficiency. Both of these methods ofreducing CO₂ can occur at the same time by optimally controlling theprocesses as described herein.

It has been found that these desired results either will not occur orwill not produce their full potential benefits unless without use ofcertain control strategies described herein. Described herein arevarious methods to selectively and continuously control combustionsystems to reduce carbon dioxide and other undesirable emissions whileimproving efficiencies. In addition, optimization of the processparameters provides added benefits in CO₂ and fuel use reduction.

Initiating the processes incorporating features of the invention isaccomplished by delivery of one or more of the atoms, or compoundscontaining such, referred to herein as catalysts, listed in Table 1.These catalysts have been found to also act to a greater or lesserextent as inhibitors or moderators at different concentration levels sotheir use requires a level of control governed by adequateinstrumentation and specific information for predicting performanceresults. Certain of the catalysts can be fed into the combustion chamberwhile others are produced in the reaction zone by the actions of othercatalysts and combustion conditions. These same catalysts can alsomoderate or retard the beneficial reactions if used at non-preferredconcentrations. Adequate levels of the desired results are produced withappropriate control techniques described herein. It should be noted thatthe designation “catalyst” is selected for description of the materialsused in the process even though the common definition of catalyst in theliterature may not properly describe the effect actually seen. Forexample hydrogen and helium may not be generally considered as catalystby those skilled in the art; however, it has been discovered that theirpresence in the described process under proper operating conditions canprovide a beneficial result similar to generally recognize catalystsunder used under similar operating conditions.

TABLE 1 Catalysts Beneficial To The Process Hydrogen Helium BoronLithium Beryllium Magnesium Potassium Sodium Chlorine Strontium Argon

The steps followed in the processes being described herein deal withcontrolling and regulating a complexity of interactions in gas andplasma states of fossil fuel combustion. They have also been found towork under different conditions.

In a preferred embodiment, initiation of the reactions within the scopeof the invention is accomplished by the delivery of lithium compounds,including but not limited to lithium acetate, lithium nitrate. Forexample, a preferred concentration of the lithium atom is 15% to0.00000005%, preferably 5% to 0.00000005%, and most preferably 7 to 35parts per billion lithium based on the quantity of the fuel and airsupply delivered to the combustion zones. Higher concentrations have notbeen found to be less beneficial in some instances but some lesserbenefits are still produced with higher concentrations. These samepreferred ranges of concentration also apply to magnesium, beryllium,sodium, potassium and boron compounds.

The catalyst can be introduced to the hot combustion zone using variousdifferent delivery mechanisms. Suitable techniques include, but are notlimited to, delivery as an additive to the fuel, injection as a hotvapor into the combustion chamber, introduction into the combustion airsupply stream, use of pre-coating insulating refractory, vaporizers, foggenerators and misters to inject catalyst into the combustion processstream, direct insertion into combustion zones as a solid which thenevaporates to coat chamber surfaces and combinations thereof. Oneskilled in the art, based on the teachings herein will readily recognizethat there are other procedures that can be used to accomplish deliveryof the catalysts to the combustion chamber to achieve the appropriateconcentration ratios of lithium, or other catalysts, atoms into thecombustion vapor-plasma phase. The objective is to establish effectiveratios in the vapor-plasma phase by controlling feed rates with theflame vaporization rate. This is balanced against condensation of thesevapors on cooler surfaces of the hot zone and then the re-evaporationfrom those cooler surfaces with radiant energy from the combustion flameand other radiant sources and with energy from highly energeticcollisions of a wide assortment of particles and molecules. Fossil fuelscoming from deep in the earth are known to include inherent traceamounts of radionuclides as well as other materials that also influencethe plasma activities. Considering the continuous evaporation andcondensation in different temperature zones, the complex soup ofelements involved, various radicals and trace elements present,different fuels, possible catalysts and chamber deposits there are amultitude of possible options available and approaches for optimizationthrough monitoring conditions and various combustion adjustments andcatalyst injection adjustments.

The bottom line objective is not necessarily to control the quantity ofcatalyst delivered to the combustor, but to control that delivery rateto obtain the desired concentrations in the combustion zone plasma.Diluents can be used to achieve desired mixing ratios, with theobjective being to deliver the lithium, other alkali metals or otherdesired catalyst, into the hot combustion zone where it exists as avapor. For example the lithium can be delivered as a solid, liquid, gasor plasma and in any compound. However, inorganic compounds arepreferred as organic materials, such as soaps, tend to leave undesirableresidues. Some diluents useful for accomplishing this for variousdelivery systems, especially for fuel borne delivery techniques include,but are not limited to water, water based miscible mixtures, a solutionmiscible in water, emulsions, hydrocarbons such as aliphatic,cycloaliphatic, paraffinic, olefinic, aromatic, synthetic oils, ethanol,isopropyl alcohol, methanol, monohydric alcohols, polyhydric alcohol,aliphatic alcohols, alicyclic alcohols, 2 ethyl hexyl nitrate (2EHN) andDi pert 3vtal peroxide to name a few.

Alkali metals in the form of paraffin blocks as well as soaps andorganometallics are effective. The objective is to produce lithium ionsin a vapor or plasma. Further, formation of the ion in the combustionplasma is not necessary as the ionization of the catalyst can begenerated in ambient air at room temperature and then delivered to thecombustion plasma. One preferred method of precision control ofinjection rates, for example for vehicle and diesel applications, is theuse of programmable delivery cartridges similar to those used forink-jet applications because they can be precisely controlled byprogramming as part of a computerized system designed with thecapability to measure and optimize system performance at extremely lowdelivery rates.

Mixing ratios, based on the delivery of a quantity of lithium orelemental alkalis in the compound, being used are set forth below inTable 2. The mix is in parts per billion based on the weight of fuelbeing burned

TABLE 2 Parts per Billion Lithium in the Fuel Broad range 4,000 to 15Preferably 1,000 to 50 Most preferably   500 to 100

The mixing ratios are based on the presumption that that there is nowater in distillate fuels, such as gasoline and diesel, being used.Alcohols such as ethanol and isopropanol as well as glycolic acid can beused. Certain fuels like residual oil and coal can be treated with waterbased solutions because so little is used. With natural gas, a water mixusing these ratios can be vaporized in the combustion air being carriedto the combustion zone. With various different types of coal, variouswater based drips and mists can be used. When seasoning occurs less andless catalyst is required. For example, when the operating chambersbecome “seasoned” and system optimization is approached; less catalystcan be delivered. Adjusting to this with gradually declining injectionratios is one of the control method described herein. If the quantitiesof catalyst delivered and the residual levels are not properlycontrolled the reactions can be turned off as a result of too muchcatalyst being present. Adjusting delivery with gradually decliningratios is a control method described herein.

Uniform mixing and interaction of active species in the plasma and vaporzones is accomplished by insuring the adequacy of the turbulence of fueland air mixing in the precombustion zone and as combustion occurs in thegas phase and plasma phase. The activity in the gas phase and ion phaseis on the order of billions of collisions a second. Activated plasmasare created with an abundance of free radicals and ion activities andwhen properly controlled cause the unique and useful products of thisinvention.

As set forth herein, lithium has been found to be effective for reducingCO₂ while overcoming a major concern about oxidation characteristics.Lithium nitrate, one of the prime candidates for reducing CO₂ absorbsmoisture readily. This property can be used to great advantage inovercoming the oxidizing effects of its dry powder form. For example, itcan be mixed with isopropyl alcohol and applied to coal. The alcoholthen evaporates leaving behind a coating of lithium nitrate on thesurface of the coal which then absorbs moisture and disappears into thecoal, making it indistinguishable from other untreated coal. Alternatelyit can be treated by simply sprinkling some lithium nitrate on the coaland letting its natural property of absorbing moisture complete thecoating process. Alternatively, a water solution can be sprinkled orspraying to produce a pre-coated coal. Various carriers can beenvisioned knowing this simple characteristic, lithium nitrate andmoisture absorbed by it will adhere to the surface of the coal, andbecome combined with the “fixed” moisture in the coal. This is a simplemeans to overcome the oxidizer characteristics of dry lithium nitrate aswell as a safe way to meter the catalyst.

Activated plasmas involve an abundance of free radicals, monatomiccollisions and other ion activity. When properly controlled and mixed,the unique and useful products of this invention are produced.Interaction of active species in the plasma and vapor zones isaccomplished by insure adequate turbulence of fuel and air mixing andvaporization of the catalysts. The activity in the gas phase and plasmaphase is on the order of billions of collisions a second which is one ofthe primary keys to these processes.

Typically combustion chambers are surrounded by various types of hightemperature insulating materials to deal with high temperature andradiation from the flame and hot combustion gases. The cooler furnacewalls of boilers are designed to facilitate the transfer heat to workingfluids such as water and steam. In engines the cooler cylinder walls andother metal parts are designed to contain high pressure spikes producedby hot combustion. These cooler boundaries chill the hot combustiongases forming boundary layers of catalysts with temperatures go fromextremely hot to relatively cool, and the combustion mixture varies froman ion plasma to vapor to liquid to solid for the catalyst in microseconds and at very short distances, each phase contributing to thedispersion and concentration of the lithium and other catalyst ions inthe plasma phase in some way.

The lithium boiling point is 2,448° F. (1,342° C.), melting point is356.97° F. (180.54° C.) and it provides varying levels of vaporpressures at temperatures found in each phase, even in the solid state.Most commonly, the adiabatic combustion temperatures of fuels are around3,992° F. (2,200° C.) for coal, around 3,902° F. (2,150° C.) for oil andaround 3,632° F. (2,000° C.) for natural gas. These flame temperaturescorrespond to usual ambient inlet air and fuel temperatures for λ=1.0,which is the symbol representing the stoichiometric combustion ratio.

In the combustion and other environments described herein the lithiumcatalyst is transformed into all of the four classic phases of matter;the gas phase through high temperatures and vaporization, the solidphase when condensed on cooler surfaces, in a liquid phase due toliquefaction during cooling and heating processes and in a plasma stateat higher combustion temperatures. These various states of matter willoccur depending on the pressure and temperature maintained at anyparticular point in the process. Each phase plays an important part inthe establishing the preferred concentration where the process takesplace and where each atom, ion and molecule experience over 10 billioncollisions a second. Combustion is a radical chain reaction where manydistinct radical intermediates participate. There are a great variety offuel radicals and oxidizing radicals in the process. Such intermediatesare short-lived and many have not been isolated. Another importantcontrol is that, unlike gases, plasmas self-generate magnetic fields andelectric currents, and respond strongly and collectively toelectromagnetic forces. The presence of these fields and forces alterthe interactions of nuclear forces and coulomb forces which in turncreate additional interactions.

Table 3 lists typical flame temperatures that can be expected withstandard burners in typical installations. The temperature determinesthe diffusion capability and rate of catalysts into the gaseous orplasma zones of combustion processes and is one of the key factors inthe controlling the processes described herein.

TABLE 3 Excess Air Flame Temperature Relationship Temperature Degrees F.Natural Oil Oil Excess Air % Gas Propane #2 #6  0% 3,400 3,700 3,8004,000 25% 2,900 3,100 3,200 3,400 50% 2,500 2,600 2,800 2,900 75% 2,3002,300 2,400 2,600 100%  2,000 2,000 2,200 2,300

A second important factor is the equation for radiant heat transfer:

Q=ρ S T⁴

where Q is Btu/hr

-   -   ρ is the Stefan-Boltzman constant: 1.17×10−9 BTU/sq-ft-hr    -   S is the surface area, sq ft    -   T is absolute temperature F+460

It can be seen from this equation that the higher the temperature of theflame, the more exponentially intense the radiant heat transfer is,which in turn influences the evaporation rate of condensed catalyst inthe reaction zone. Flame temperatures shown in Table 3 and heatabsorption by chamber components can significantly alter theconcentration of the catalyst in the combustion plasma.

Collision activity plays a significant role in the combustion process.When reactant particles collide, only a certain fraction of the totalcollisions have the energy and impact angles to connect effectively andcause the reactants to transform into new products. This is because onlya small portion of the molecules or atoms have enough energy and theright angular orientation at the moment of impact to break existingbonds and form new ones. However, with particle activity in terms ofbillions per second and the absolutely huge populations involved, evenlow statistical probabilities become possible. The minimal amount ofenergy needed for this to occur is known as the activation energy. Ifthe collision is successful, the elements react with each other.However, if the concentration of at least one of the elements is toolow, there will be fewer particles for the other elements to react withand the reaction will happen much more slowly. As temperature increases,the average kinetic energy and speed of the molecules increases but thisonly slightly increases the number of collisions. The rate of thereaction increases with temperature increase because a higher fractionof the collisions overcome the activation energy. If moderating andhigher mass species are present they will absorb the aggregate collisionenergy available reducing the number of successful collisions.Therefore, a continuous analysis of the combustion products formed bythe process is desirable for determining and imposing effective processcontrol. Lithium is a preferred catalysts because it has unusually lowbinding energy compared to the next lighter and heavier elements, heliumand beryllium. This means that lithium alone among the light elementscan produce net energy through fission events. This provides a goodprobability of kicking off additional reactions and additional chainformation, producing the results measured in the experiments describedin the included figures and tables. It was found by measuring particleactivity that alpha particles and protons were being created by thisprocess using special instruments designed for such measurements. Theirvoltages and reaction temperatures are listed in Table 4. Also listedare experimental results measured in combustion phase experimentssimulating the combustion experiments described herein. This is not tosay that the results are not catalytic, it may that this data is in factan explanation of the catalytic processes.

TABLE 4 Degrees F. Alphas 8.6 MeV 1.55E+07 Hydrogens 5.4 MeV 5.40E+06Degrees F. 8 KeV  14,000 304 KeV 550,000 800 KeV 1.4 Million 1,600 KeV2.9 Million 3,200 KeV 5.8 Million 4,000 KeV 7.2 Million 4,088 KeV 7.4Million

The particles activated in the plasma have sufficient energy to cut andseparate the long hydrocarbon chains of fossil fuels into smallercleaner burning chains. Instant break up of these chains and ionizationproduces a better more efficient burn. Accordingly, the activated plasmazone can be used to rapidly break the hydrocarbon chains and moleculesinto smaller chains and molecules so that they can be more efficientlycombusted. In coal combustion for example this leads to intensivedevolatization producing CO, CO₂, H₂, N₂, CH₂, C₆H₆ and others,accelerating the oxidation of volatile fuel combustibles.

The information in Table 4 is useful in explaining the seasoningphenomena, especially when the efficiency improvements and pollutionreductions extend for long periods after the catalyst injection ceases.The term “well seasoned” is meant to convey that the interior surfacesof the combustion chamber have been exposed to the catalyst reactionsand trace levels of various other elements typically found in fuels.Even after thorough cleaning the positive effects continue indicatingthe metal combustion chamber walls have acquired a long term “seasoned”state. Particle activity caused by select catalysts produces extremelyhigh temperature events causing the catalysts to become embed andsometimes fused or alloyed in the chamber's base materials on atomic andmolecular levels. Additionally, catalyst particulate condensation andadherence to chamber surfaces and embedded in microscopic crevices andinter-granular spaces of metals and insulation then serve as originpoints for the enhanced activities of this catalyzed process.

When attempting to determine concentrations of the catalysts in the hightemperatures of the gas phase, concentration values cannot be directlymeasured because at the lower temperatures at which gas analysis systemsoperate the catalysts being measured will condense. For example, thelithium collected in the gas samples will condense into liquid or solidphases. This therefore requires that control parameters must be inferredfrom the measurable results of other materials present as a gas, such aschanges in CO₂, NOx, SOx, CO, oxygen, or measurement of monatomicspecies from the gas and plasma phases. These pollutants and othermonatomic element concentrations as well as other gases and moleculeswill serve as criteria for process control through inferred levels ofcatalyst concentration as determined by results produced. An importantcriteria is that the process described herein produces lower levels ofCO₂ and these lower levels can be monitored controlled and optimized.The reduction of all pollution levels including CO₂ have beendemonstrated using this same process in many tests as indicated in theattached figures.

Because of the complex nature of the reactions occurring a number ofmaterials were found to act as catalysts to this process. However, thesesame compositions and elements can also moderate and even turn off thebeneficial reactions. Adequate levels of the desired reactions can beproduced by controlling concentrations of the species which favorablyregulate the process in conventional combustion power systems and othergas environments.

Following is a list of species (as elements or parts of compounds) thathave been found to be beneficial to the process for producing improvedresults, and are therefore considered to act as catalysts.

-   -   1. Hydrocarbon fuels: oil, gas and coal    -   2. Ambient air, Nitrogen, oxygen and trace gases.    -   3. Lithium    -   4. Alkali metals    -   5. Hydrogen    -   6. Helium    -   7. Water, hydrogen and oxygen and trace elements.    -   8. Ethanol and other alcohols used as carriers    -   9. Isopropyl alcohol and other petroleum products and solvents        used as carriers    -   10. Photons    -   11. Boron    -   12. Beryllium    -   13. Background radiation.    -   14. High voltage sparks and electromagnetic fields, coronal and        other high energy discharges

Some of these species, for example alkali metals, used in this processhave been found to be both initiators and inhibitors in the high energyatmosphere, acting to reduce or prevent the process performance undercertain conditions.

On the other hand, the following materials have been found to have anegative influence on process results and therefore should be avoidedbecause of their moderating influence:

-   -   1. Absence of helium    -   2. Nitrogen    -   3. Oxygen    -   4. Magnesium    -   5. Aluminum    -   6. Silicon    -   7. Sulfur    -   8. Elements with higher atomic weights, especially beyond iron        and chromium on the Periodic Table.

At least 73 elements found in coal-fired plant emissions are distributedin millions of pounds of stack emissions each year. They include:aluminum, antimony, arsenic, barium, beryllium, boron, cadmium, calcium,chlorine, chromium, cobalt, copper, fluorine, iron, lead, magnesium,manganese, mercury, molybdenum, nickel, selenium, silver, sulfur,thorium, titanium, uranium, vanadium, and zinc. To improve combustionresults the presence of these naturally occurring materials should bemonitored and controlled as they can have a negative effect on theprocess.

It has been found that use of high voltage spark systems along with thelithium catalyst was effective in producing pollution reductionsespecially CO reductions in the 90% range. High voltages (10,000 to over25,000 volts) were also associated with increased oxygen levels andincreased efficiency and therefore qualifies as an initiator andcatalyst as well as many other high voltage sources such as uranium,thorium and polonium.

Provided herein are representative examples using processesincorporating features of the invention. These processes are set forthto aid in an understanding of the invention but are not intended, andshould not be construed, to limit in any way the invention as set forthin the claims which follow thereafter.

EXAMPLE 1

Two vehicles, one a diesel powered farm tractor and the second agasoline powered pick-up truck were tested using the process. For thegasoline powered Dodge pickup truck, a mix of 3.3 milliliters per gallonof gasoline was used. The isopropyl additive mix, contained 30 grams oflithium nitrate per gallon. This was poured straight into the fuel tank.The gas powered light truck first produced a drop in CO₂ of 52%, andthen it went to a 93% after accumulating about 50 road miles. Theexhaust gas samples were measured near the engine exhaust before thecatalytic converter. For the diesel tractor, a mix of 5 milliliters pergallon of diesel was used from the same isopropyl additive mixcontaining 30 grams of lithium nitrate per gallon. This was also pouredstraight into the fuel tank. Exhaust gas samples were drawn directlyfrom the engine exhaust. The diesel engine's CO₂ level dropped by 94%from baseline tests after catalyst treatment after running for about anhour. Gas samples were tested both on-site and at a near-by laboratory.

EXAMPLE 2

A 5 month test was conducted on a natural gas fired boiler rated at 12million BTUs per hour which providing steam for utilities service at aUC Irvine. The lithium nitrate in this case was mixed in water and fedinto the gas burner using a humidification system with an averageconcentration of the lithium nitrate to the average natural gas burn of5 parts per million. A series of 7 analysis towards the end of thistesting period indicated CO₂ averaging 73% below theoretical. The plantinstalled oxygen analyzer; a portable Combustion Analyzer and a set ofabsorption chemical CO₂ instruments were used for the test. In one case,at a constant 2.2% oxygen reading, the theoretical % CO₂ for natural gasshould have had a corresponding value of 12%, but the actual value ofCO₂ averaged a much lower 3.13% indicating the drop in CO₂ of 73%.

EXAMPLE 3

Drop-tube combustion testing of coal samples using a targetconcentration for the catalyst of 5 parts per million using a water mixdripped coal samples provided the follow results:

-   -   Carbon Dioxide (CO₂) reductions of 30% and 53%    -   Nitrous Oxide (NO) reductions of 58% and 77%    -   Sulfur Oxide (SOx) reductions of 8% and 40%

EXAMPLE 4

Test conducted using ASTM D-240 the Standard Test Method for Heat ofCombustion of Liquid Hydrocarbon Fuels by Bomb calorimeter. This testutilized 1 milliliter of a lithium isopropyl mix producing aconcentration of 2.6 parts per million in each fuel. This compositionproduced the following results:

Fuel Energy Increase Gasoline 84 Octane 7.0% Gasoline 97 Octane 8.4%Kerosene 9.5% Diesel #2 10.0% Ethanol 10.3%

EXAMPLE 5

Tests conducted using ASTM D-5865, the Standard Test Method for GrossCalorific Heat Value of Coal and Coke. Using an aqueous solution with atarget of 5 parts per million lithium nitrate produced the followingresults:

Before After Percent Btu/lb Btu/lb Change 9,126 11,134 22% 8,359 12,48950% 7,247 14,759 104% 

EXAMPLE 6

Carbon furnace test, with 41 baseline measurements validating the testbed, all indicated CO₂ within the proper 19.6% range for anthracitegrade fuel. The lithium catalyst dissolved in water was used to wet downthe carbon briquettes. Concentrations varied from a few parts permillion to 1-5% lithium nitrate. The object of this test was to verifythat CO₂ could be reduced with the catalyst. The test series produced 23successful test runs indicating lower CO₂ levels. The highest CO₂reduction recorded was 47% with a CO₂ level reduced to 10.3% from 19.5%.These tests shown below clearly indicated that CO₂ can be eliminated inthe combustion phase of fossil fuels.

Follow up test with 10 grams of potassium catalyst in the form ofseveral 2 to 4 gram nuggets were dropped on the fuel bed duringcombustion followed by 22 additional test runs which produced a maximumCO₂ reduction of 31% ,down to 13.5% CO₂ from the 19.5% baseline. Theobject of this experiment was to coat the furnace walls and interior ofthe combustion system with potassium, (K-40) to increase the activationarea.

Carbon dioxide Reduced in Combustion Plasma % CO₂ standard foranthracite is 19% to 20% The catalyst in this test series produced muchlower levels. New CO₂ % CO₂ Comparable Fuel Type Test No. ReductionLevel of New % CO₂ Level 1 41% 11.4 Natural Gas 2 32% 13.2 Natural Gas 330% 13.6 Propane 4 22% 15.2 Gasoline 5 22% 15.3 Kerosene 6 20% 15.7 #2Diesel Fuel 7 19% 15.8 #4 Fuel Oil 8 19% 15.9 #4 Fuel Oil 9 16% 16.4 #5Residual Oil 10 14% 16.8 #6 Residual Oil 11 11% 17.4 Tar & Pitch 12  9%17.8 Tar & Pitch 13  7% 18.1 Bituminous Coal

EXAMPLE 7

FIG. 1 shows results measured during a typical batch carbon burn off.During each of these tests the fire zone was closely observed as itburned down, producing the accompanying combustion intensity profile asindicated by temperature and visual indications relative to the carbondioxide levels which were measured at the same time.

EXAMPLE 8

FIG. 2 shows test results at an automotive emissions testing laboratoryusing Federal Test Procedure protocol. A reduction of carbon monoxide of37% and a reduction of carbon dioxide of 5.4% was produced. Also fuelefficiency increased by 8.4% using a 5 parts per million concentrationof lithium nitrate dissolved in ethyl alcohol mixed with the test fuel.

EXAMPLE 9

Results of test using alkali metals other than lithium are shown inTable 5. Alkali metals other than lithium can be used in the reaction toreduce CO₂. Table 5 shows results when magnesium nitrate and potassiumnitrate compositions were added to the fuel. The vehicle was a 1966 FordMustang which had no catalytic converter or Engine Control Unit.

TABLE 5 Carbon Carbon Test Monoxide % % Change Dioxide % % ChangeBaseline 1.75 13.1 Fuel 2 1.36  −22.3% 9.54 −27.2% Fuel 3 1.39 −20.57%11.34 −13.4%The baseline fuel was premium gasoline with 50 ml of methanol and 100 mlMTBE per gallon. Fuel 2 was baseline fuel plus 0.625 grams MgNO₃ pergallon. Fuel 3 was baseline fuel plus 0.33 grams KNO₃ per gallon.

EXAMPLE 10

FIG. 3 shows CO₂ test results for 264 test points. Variousconcentrations of lithium and potassium were used during these tests;the air-fuel ratios were also changed during the batch burns. Theintensity of the burn and levels of seasoning of combustion zone andexhaust system were also varied. These tests were used to establish thedynamics of this process and to identify the control factors needed tooptimize CO₂ reductions during a complex and varying combustionconditions. The results of this test were used to establish controlmeasures for optimization.

EXAMPLE 11

FIG. 4 shows CO₂ reduction during burn tests of anthracite gradebriquettes. The highest levels of CO₂ reductions occurred during themost intense and hottest period of the burn off. This is the period ofthe most active boil off of the lithium accompanied by the mostturbulent mixing in the gas phase revealing important control elementsto be used for optimizing the process.

EXAMPLE 12

FIG. 5 shows the typical CO₂ reduction obtained in a series of 264 burnsof high carbon briquettes. The highest levels of CO₂ reductions occurredduring the most intense and hottest period of the burn off. The additionof potassium activator in data runs 29-45 produced significantly higherCO₂ reductions. Additionally, the use of the potassium K-40 activator ina well seasoned test furnace produced significantly greater CO₂reductions then in the tests shown in FIG. 4. By “well seasoned” ismeant the interior surfaces of the furnace had a thin layer composed ofcarbons, lithium and other catalysts as well as trace levels of variousother elements typically found in fuels and the K-40 activator. FIG. 6is a different graph showing the benefit of using a potassium activatorto produces a greater CO₂ reduction in batch type carbon burn off. Otheractivators such as polonium and thorium have also proven to be effectivein carbon dioxide reduction.

FIGS. 7 and 8 are graphs that demonstrate that the reduction in CO₂generation increases with the volume of the surface of the combustor andthe roughness of the surface, both factors resulting in a greateraccumulation of the catalyst on the surface. The reaction zone walls areusually much cooler than the combustion phase. Temperatures as high as3,500° F. exist near the burner with oil and to 2,500° F. for gas fuels.The melting temperature for lithium is 357° F. and the boilingtemperature is 2,448° F. so lithium will be in a vapor phase, liquidphase and the solid phase at different locations depending on localizedgas and metal temperatures. Vapor pressures vary with temperature withthe lithium solidifying in the cooler regions of combustion chamber.Each combustion process has varying wall temperatures at differentlocations so this becomes a very complex issue when the differencesbetween diesel engines, gasoline engines, furnaces, boilers and gasturbines are considered. Added to this is the fact that different fossilfuels burn at different temperatures and local air to fuel ratios alsoproduce different flame temperatures. Larger reaction chambers will havelarger sweet spots that are most favorable to optimized results. FIG. 7shows that as larger optimized zones occur, more effective results canbe created by increased time in the sweet spot. In regard to FIG. 8, ifthe condensed lithium fails to make contact directly on a cooler metalsurface due to scale or deposits it will be at a temperature greaterthan the cooler metal surfaces of the combustion chamber and will have ahigher vapor pressure or be melted or vaporized having exceeded theboiling point. A roughness in the surface is more likely to capturecatalyst particles and resist cleaning activities such as maintenancecycles and soot blowing in the case of units burning residual fuels andsolid fuels such as coal. Acids formed by combustion processes may haveetched metal surfaces and formed micro crevices which can harbor minuteparticles of the catalyst. Extended periods of reduced CO₂ and pollutionand prolonged periods of significantly higher efficiency have beenproduced by this roughened surface condition resulting in catalystretained on combustion chamber surfaces.

The Dry Flue Gas Combustion Chart (FIG. 9) published by Babcock & Wilcoxin the book, Steam Generation and Use, Chapter 9, is a useful source forinterpreting and understanding experimental results relating to thereduction of CO₂. This chart was developed when the Orsat three gasanalyzer [O₂, CO₂ & CO] was the primary combustion gas analysis tool.Most modern combustion analyzers used for boiler testing do not measureCO₂; they do a mathematical conversion from oxygen readings because thisrelationship is considered to be constant and unalterable. That is whyboth modern instruments and older absorption chemical analysis were auseful cross check for CO₂ verification as they both measure CO₂ but byindependent means. The darker lines drawn on FIG. 9 define the zone ofcorrect CO₂ measurements for Anthracite coal combustion from 19.3 to19.85 for the ultimate CO₂ value for a stochimetric burn at zero oxygendilution. If instruments accurately detect CO₂ levels outside of thiszone, then some change is occurring with the CO₂. Accordingly, thisgraphic serves as a precise cross-check for indications of changes inactual CO₂ emissions. The arrow to the right of the Anthracite coal zonepointing to a CO₂ level of 11.4% measured by CO₂ instruments indicatesirrevocable proof of CO₂ reduction.

FIG. 10 shows the CO₂ reductions produced in a furnace burninganthracite coal. In this case the original CO₂ value for coal was 19.5%.During testing the CO₂ value dropped to a level below natural gas to apoint where no CO₂ could be detected.

This same process, as shown in Tables 6 and 7, produces excess heat wellabove the standard Higher Heating Values for fossil fuels.

TABLE 6 Standard Test Method for Gross Calorific Value of Coal and CokeBefore After Percent Fuel Type Btu/lb Btu/lb Change Coal & 8359 1248950% Petroleum Coke Coal 9126 11134 22% Coal 7247 14759 104% 

Table 6 sets forth the data obtained in a laboratory coal testingprogram complying with ASTM D-5865, the Standard Test Method for GrossCalorific Value of Coal and Coke in a series of tests utilizing aprocess incorporating features of the invention. The tests producedincreased heat values (the “after” values) of 22%, 50% and 104%.

TABLE 7 Fuel Energy Increase Gasoline 84 Octane 7.0% Gasoline 97 Octane8.4% Kerosene 9.5% Diesel #2 10.0% Ethanol 10.3%

FIG. 11 is a graph showing over 300 boiler tests with efficienciessignificantly higher than the design values for various boilers theywere run on. As set forth below, these test demonstrate

-   -   1. The seasoning effect of catalyst and its persistence    -   2. The effect of ultra low catalyst levels producing very high        efficiency improvements    -   3. The production of oxygen    -   4. The effect of ethanol and water significantly improves        results    -   5. Very high efficiency gains    -   6. Very high pollution reductions, especially carbon monoxide

The zero baseline represents the basic efficiency for the boilers testedor, in some cases the Heat-Loss efficiency measured at the time of thetest, considered to be within 1% of the calorimetric measurements shown,usually labeled Output-Input efficiency in ASME Boiler Test Codes. Ahigh level of repeatability is shown to exist in more than 300 boilertests which have produced efficiencies significantly higher than designvalues for various boilers they were run on.

While CO₂ values were not obtained in this test series, it was foundthat there were consistent large reductions in carbon monoxide and anincrease in oxygen generation (see Boiler Tests 9-13 and 15 listed, inTable 8 below), strongly suggesting a reduction in CO₂ as follow upexperiments proved.

TABLE 8 Measured Change Percent Change Boiler test No. 9 Oxygen 3.6% to7.8% 217%  Carbon monoxide 130 to 19.7 ppm 85% Efficiency improvement7.8%  Comments: 4 hours 25 test points 10 min each no catalyst onlyethanol + water added to fuel Boiler test No. 10 Oxygen 2.7% to 9.3%344%  Nitrogen oxides 117 to 1 ppm 99% Carbon monoxide 130 to 19.7 ppm85% Efficiency improvement 12% Comments: 2.25 hours 13 test points 10min each Catalyst and ethanol + water added to fuel Boiler test No. 11Oxygen 2.5% to 8.8% 346%  Nitrogen oxides 96 to 53 ppm 46% Carbonmonoxide 281 to 19 ppm 93% Efficiency improvement 19% Comments: 7 hours40 test points 10 min each No Catalyst only ethanol + water added tofuel Boiler test No. 12 Oxygen 2.3% to 8.8% 380%  Nitrogen oxides 102 to48 ppm 53% Carbon monoxide 95 to 0 ppm 100%  Efficiency improvement 27%Comments: 7 hours 41 test points 10 min each No Catalyst or ethanolThoroughly cleaned boiler before test and replaced ceramic furnace linerBoiler test No. 13 Oxygen 2.8% to 9.2% 317%  Nitrogen oxides 115 to 48ppm 58% Carbon monoxide 70 to 0 ppm 100%  Efficiency improvement 25%Comments: 7 hours 40 test points 10 min each No Catalyst or ethanolBoiler test No. 15 Oxygen 1.6% to 2.5% 36% Nitrogen oxides 136 to 81 ppm40% Carbon monoxide 3,000+ to 0 ppm 100%  Efficiency improvement 10%Comments: 6 hours 37 test points 10 min each No additive seasoned duringtest 14

FIGS. 12 and 13 illustrate the results from Boiler test 16 and 18respectively. Referring to FIG. 12, the results in this graphic wereproduced within a boiler previously treated with catalyst. The boilerwas cleaned and no catalyst was subsequently introduced into the boiler.After an estimated 25 hours of operation without catalyst in an attemptto burn out any possible tenacious residue that might have remainedafter thorough cleaning of the chamber and replacement of the firepot'sceramic liner. During cleaning the catalyst deposits easily washed awaywith water wash down. However, the pollution reductions and highefficiency levels persisted for an additional 50 more hours of testing.The gradual increase in efficiency in FIG. 12 could not be accounted forby subsequent catalyst vapor release from the furnace walls as surfacedeposits had been thoroughly cleaned. It is noted as the temperatures ofthe furnace continue to rise during this test, the efficiency continuedto increase. A seasoning effect of metal components in the firepot zonewas suspected as the source of this phenomenon. Accordingly, the furnaceand heat exchangers were once again disassembled and thoroughly cleaned,although no deposits were observed on any components in the hightemperature zone. All fire box components were then replaced including anew metal factory supplied firebox and a new factory ceramic liner.During subsequent testing the Output-Input efficiencies returned tonormal levels shown in FIG. 13. This disclosed a different nature ofseasoning, namely metallurgical conditioning.

Referring to FIG. 13, following catalyst use only after dismantling andcleaning the boiler for a second time and after replacing its steel baseand firebox ceramic insulation, did the unit finally came back to normaland expected (lower) efficiency levels. By way of explanation the heatLoss efficiency and Input-Output efficiency should agree very closely ina well instrumented boiler as shown in this figure. The efficiencydifferences measured with the catalyst runs were well beyond the slightmargin of error experienced during this calibration test.

FIG. 14 shows the effect of combustion zone conditions on heat output.During the early tests many attempts were made to correlate performancechanges such as emissions reductions, CO₂ reduction and increased heatproduction with changes in catalyst concentration. Extensive testing anddata showed that no correlation occurred even though the lithium nitrateinjection was varied over an appreciable range between zero and 500parts per million. A correlation was discovered between combustion zonetemperature, the duration of the experiment. Additionally, the bestresults were produced after thorough seasoning of the combustionequipment combined with no new catalyst input, which becomes a moderatorat some point shown in FIGS. 16 and 17. This fact is reinforced by FIG.15 where the energy output spikes when the catalyst introduction was cutoff at the end of some early tests in an attempt to reestablish originalefficiency conditions. The boiler for this test series burned dieselfuel using a commercial power burner at steady state conditions. A longwarm up period preceded data recording to insure that thermalequilibrium had occurred before measuring changes produced by thecatalyst.

In regard to FIG. 15, certain levels of the catalyst act as a moderatoras shown in this illustration. It was noted in one boiler test theenergy producing reaction increased by 18.8% immediately after theinjection of the lithium catalyst was stopped; just prior to this thesame boiler had been operating at a 10.8% level above normal. This is anindication of a self-moderating influence. This illustrates that it isadvantageous to reduce catalyst delivery after initial benefits arenoted.

Table 9 lists improved efficiency over base line and heat outputincrease for three test series (Test 5-7) at different lithium catalystdelivery rates. Tests 5 and 7 illustrated improved efficiency even aftercatalyst delivery was stopped. During boiler test number 5 the excessenergy spiked immediately after the catalyst feed rate was cut back from185 PPM to zero. During the next 17 minutes the heat output increased by12% to 18% above the original baseline efficiency then fell off to lowerlevels. During boiler test number 7 the excess energy spiked after thecatalyst feed rate was cut back from 27 milliliters per minute to 0.During the next 30 minutes the heat output increased by 14% to 24% abovethe original baseline efficiency, then fell back to a much lowerefficiency level.

Test 6 (Table 8) illustrates a retarding effect by increasing catalystdelivery and then an improved efficiency by a reduction of catalyst toformer delivery levels. During boiler test number 6 the excess energyspiked immediately after the catalyst feed rate was cut back from 41milliliters per minute to 18. During the next 30 minutes the heat outputincreased by 22% to 24% above the original baseline efficiency

TABLE 9 Efficiency Catalyst Improvement Feed Rate Above Heat Outputml/min Baseline Increase Test No. 5 5 5% 6 7% 5 7% 7 6% 0 18%  12% 0 4%0 9% Test No. 6 19 5% 19 9% 19 5% 41 3% 18 24%  22% Test No. 7 37 3% 348% 27 8% 1 11%  0 24%  14% 0 3%

FIG. 16 shows several occasions when the excess energy caused by thecatalyst reaction peaked and then fell off after moderating influencescame into play. This is a sample from 40 recorded test runs examined. Inthis case the catalyst itself, because it was the only variable beingintroduced into the process during testing of an oil fired boiler, wasdetermined to be the cause of the moderating influence which at firstcaused higher efficiencies then caused efficiencies to diminish.

FIG. 17 shows that the efficiency peaked four different times during amonth long test of a large 500,000 million BTU per hour refinery boilerand then dropped off because of moderating influences. Because of themany influences that may be presented to the process control of thistechnology, optimum results requires the use of various analyticalinstruments such as a gas chronograph and spectrum analyzers to identifythe cause of changes and then use this information to fine tune theprocess. There are many candidate moderators which exist as traceelements and compounds in the fuel, boiler deposits, metallurgy ofboiler internals, dust composition and concentration and control roomfiring adjustments. These are in addition to carefully controlling thecatalyst species and concentrations and the combustion air supply.

In an effort to return the test boiler to its original baselinecondition it was thoroughly cleaned and a new insulating ceramic linerinstalled in the furnace area. In spite of this clean up action theefficiency remained significantly above the baseline datum under steadystate conditions as shown in FIG. 18. The higher efficiency levels hadachieved a tenacious level of permanency.

Various methods of control, relying on various types of instrumentationand observations have proven effective. As a result protocols have beenestablished to effectively control and beneficially exploited theprocesses described herein. FIG. 19 shows a step-wise optimizingprocedure used to gradually reduce carbon dioxide and pollutantemissions as well as improving efficiency. Reducing excess air in wellcontrolled incremental steps as illustrated insured safety and guardedagainst inadvertent smoke, hydrocarbon and carbon monoxide emissions andalso reduced the nitrogen and oxygen levels, which act as moderators tothe desired results, in the furnace reaction zone. This method improvedthe overall effectiveness with a minimum possibility of upsetting thecombustion process.

Controlling the optimizing process was done by implementing a series ofsmall incremental steps coordinated with checks on the results as wellas cutting back on the air fuel ratios or to reduce the lithium andother alkali catalyst which can also act as inhibitors in the gas phase.There is a fine line between measure and control, taking into accountall of the positive and negative factors of catalytic and inhibitinginfluences affecting the process. A general rule was that when an actionproduced a positive influence it was increased slightly until desiredresults tend to flatten out. It was also important to keep good recordsand watch for additional changes over time. It was expected at somepoint that an optimized performance would occur. Reductions of CO₂ didnot necessarily occur simultaneously with reductions of other pollutantsor increases in efficiency. This process offered an opportunity forrecognizing improvements which may or may not occur under the samecontrol conditions considering the complexity of the variables availablefor manipulation. This also offered flexibility in results which is oneof the advantages of this process.

FIG. 20 shows the step wise reduction of combustion air which in turnreduces the inhibiting effect of the air on the catalyzed combustion.Using this procedure, combustion air can be drawn down below originalstoichiometric ratios without producing the usual end point effects ofsmoke, carbon monoxide and hydrocarbon losses while increasing positiveresults of reduced CO₂, pollution and higher efficiency. FIG. 20 alsoillustrates an important safety feature of the process; specifically,the combustion can be turned off quickly by sharply increasing theexcess air at the burner. This can be accomplished automatically usingcombustion safety controls when the fuel valves are closed. The controlsystem goes through a post combustion purge cycle which uses thecombustion air supply to sweep the furnace and boiler of any residualcombustion gases or fuel.

As indicated above, extremely small amounts of the catalysts need bedelivered. Further, once the combustion chamber is seasoned, or initialquantities of the catalyst are delivered in conjunction with the fuel,because of residual effects of the prior delivered catalyst and the factthat excess quantities of the catalyst may eventually retard thebeneficial effects of the presence of the catalyst it is important tomonitor the combustion process to maintain an optimum effect. Oneskilled in the art will recognize that it may extremely difficult tomeasure and monitor the amount of the catalyst present in the combustionzone because of the minute catalyst quantities present and the hightemperatures existing. However, suitable techniques and instrumentationexist for continuously monitoring the flame temperature and the presenceof various gases in the exhaust stream including, but not limited to CO,CO₂, oxygen and NO_(x). At the same time, the exhaust should bemonitored to determine if an increase in other carbon based pollutants,trace elements in the fuel or unburned fuel show up in the exhaust. Datapresented herein show that use of the catalyst under optimum conditions,when compared with the same equipment burning the same fuel without thecatalyst present (a base line), results in elevated combustiontemperatures and oxygen levels and reduced CO and CO₂ levels.Accordingly, following exposure to the catalyst in a seasoned combustionchamber and/or by adding the catalyst in any manner, such as in thefuel, in the combustion air feed, in a solid form to the chamber, etc,when desired operating conditions are reached the catalyst feed can beadjusted so as to maintain those desired operating conditions. Forexample, if CO and CO₂ levels increase and temperature and oxygendecrease catalyst can be added to reestablish desired operatingconditions. As excess oxygen appears in the exhaust stream, it is alsopossible to reduce the air feed to the combustion chamber as such excessoxygen is a sign that the combustion process is running more efficientlyand less oxygen is being utilized in producing CO and CO₂.

More particularly, a process is described for the combustion of acarbon-based or hydrocarbon fuel in a combustion chamber using thecatalyst or catalysts described herein while maintaining or increasingthe efficiency of said combustion and reducing the CO₂ and the amount ofpollutants produced by said combustion, when compared to a controlprocess, are reduced. In a first embodiment an initial quantity of acatalyst is fed to the combustion chamber simultaneous with feeding ofthe carbon-based or hydrocarbon fuel and an oxygen containing gas at aninitial fuel/gas ratio to form a catalyst/fuel mixture followed byigniting said catalyst/fuel mixture to produce a flame and an exhauststream. The combustion products and temperature of the flame aremonitored until a maximize efficiency is obtained. That maximumefficiency can be indicated by a maximized BTU output, horsepowergeneration, increased stem production, etc. or, for example, the flametemperature. An increased flame temperature is generally translatable toan increased efficiency of the combustion process for that combustionchamber as it indicates that more energy is being generated from thefuel fed to the combustion chamber. The components of the exhaust streamobtained during the combustion are also monitored during the flameinitiation process as well as when the maximize flame temperature isreached. When the factor being monitored as an indication of optimumoperation, such as a maximized flame temperature is reached, thecatalyst feed is reduced, and optionally periodically adjusting. Thequantity of catalyst subsequently delivered is generally less than theinitial quantity fed along with the fuel mixture in order to maintainthe flame at a desired temperature. Typically, one or more of thecomponents of the exhaust stream that are monitored comprise one or moreof CO₂, CO and oxygen. However, other components can be monitored so asto generate an exhaust stream containing less pollutants in a systemoperating at a greater fuel efficiency. It is also possible to reducethe amount of oxygen containing gas introduced into the combustionchamber to increase the fuel/gas ratio while maintaining the flame at orabout the desired temperature and the CO₂ concentration at a level lessthan measured in a comparable control burn.

In a second embodiment, the combustion chamber is first seasoned byfeeding just the catalyst. The process described above is then conductedwithout adding additional catalyst or adding sufficient catalyst to thefuel mix or the combustion chamber to maintain the maximum flametemperature and reduced CO₂ production.

In an embodiment for burning coal, a method has been developed to treatthe coal with lithium and/or other alkali compositions to produce theCO₂ reductions, overcoming a major concern about oxidationcharacteristics. Lithium nitrate is a preferred composition forintroducing alkali metals. Some compounds like lithium nitrate absorbmoisture readily from the atmosphere. This property can be used to greatadvantage in overcoming the oxidizing effects of its dry powder form. Ahighly concentrated mixture of lithium nitrate and isopropyl alcohol wasadded to a batch of rice sized anthracite coal. The alcohol wasevaporated leaving behind a coating of lithium nitrate on the surface ofthe coal which then absorbed moisture, making it indistinguishable fromuntreated coal. Treating the coal can also be accomplished by simplysprinkling some lithium nitrate on the coal and letting its naturalproperties complete the coating process. Alternatively, it can beapplied by sprinkling or spraying a pre-formulated water solution on thecoal. Various different carriers can be envisioned based on thehygroscopic nature of lithium nitrate which will be absorbed by and willadhere to the surface of the coal, and become combined with the “fixed”moisture in the coal. This is a simple means to overcome the oxidizercharacteristics of the dry form of the material.

Internal combustion engine testing was conducted on an enginedynamometer test stand, with calibration traceable to NTIS standards.The engine used was a Pontiac LR-8 with an open loop engine controlsystem. Raw engine exhaust was measured. The data in Table 10 is anaverage of tests run at three loads, namely low (1,000 rpm), medium(2,000 rpm) and high (3,000 rpm).

TABLE 10 Engine Dynamometer Testing Carbon Nitrogen MonoxideHydrocarbons Oxides Oxygen Baseline 0.413 PPM 1147 PPM 1,628 PPM 0.613%With Reaction 0.10 PPM 857 PPM 3,442 PPM 2.495% Percent Change −76% −25%+111%  307%

Although carbon monoxide pollution dropped by 76% and hydrocarbonsdropped 25%; an unexpected discovery was the increase in oxygen in theexhaust by 307% and nitrogen oxides by 111%. The increase in nitrogenoxides is accounted for by the very high energy (temperature) ofparticle activity in the combustion zone. Nitrogen oxide formation is afunction of time and temperature. The engine settings affecting time andtemperature, load and spark timing, were held constant. The high energyand temperature of the reaction accounts for the higher NOx. It was alsoobserved that higher oxygen levels should normally tend to reduce NOx byproducing lower flame temperatures. This oxygen is formed by thereaction and has shown up in many tests when no adjustments were made tothe mechanical aspects of the air/fuel ratio control. This additionaloxygen available in the combustion zone facilitates cleaner and moreefficient combustion as dry gas losses are lowered by less heat beingcarried away in the exhaust gases by the 80% nitrogen accompanying theair which is normally the source of oxygen for combustion. In the pastlaboratory testing of the combustion process has detected and identifiedhigh levels of particle activity. With the catalysts described hereinand particularly lithium under controlled conditions. The presence oflarge quantities of high energy particles and Swift Protons” with thekinetic energy suitable for shearing long hydrocarbon chains, such asschematically shown in FIGS. 22 and 23 were observed.

Highly excited protons and other active particles activated by thecatalysts have the capability to shear long and complex hydrocarbonchains, as well as combustion pollutants such as CO₂, CO, NO, NO₂, SO₂,SO₃, reducing them to smaller, more benign, cleaner burning molecules.This effect is also suitable for clean up of toxic and radioactivecontamination, including mountains of commented coal ash and billions oftons of CO₂ produced every year.

The highly energetic particles produced by catalyst advance beyond theflame front and shatter complex fuel molecules creating an extremelyfast moving ionizing zone and an even-burning flame front activity.Experimental methods of control, relying on various types ofinstrumentation and observations have proven effective.

It follows from the forgoing description that processes and methodsincorporating features of the present invention include a method whereinthe internal surfaces of a combustion chamber exposed to combustionprocesses of hydrocarbon fuel powered systems are conditioned by lithiumnitrate to enhance the efficiency of the combustion process, saidmethods comprising providing lithium nitrate dissolved in a hydrocarbonfuel to said hydrocarbon fuel powered system and combusting saidhydrocarbon fuels.

The fuels contemplated for use in the present invention are set forthin, but are not limited to, the following standards which includehydrocarbon fuels such as gasoline, diesel fuel, biodiesel fuels, andfuels blended or containing alcohols as described in the following ASTMspecifications. The fuels contemplated for use in the present inventionare typically liquid hydrocarbon fuels in the gasoline boiling range.Gasoline fuels are supplied in grades and designations defined by theAmerican Society of Testing and Management, ASTM D396-09a Specificationfor Fuel Oils, while ASTM D4814 Standard Specification for AutomotiveSpark-Ignition Engine Fuel defines fuel hydrocarbon compositions andblends with oxygenates. Motor gasoline typically have boiling rangeswithin 70-450° F. while aviation gasoline typically have boiling rangeswithin 100-300° F. Specifications used to define fuel-alcohol blendsinclude ASTM D5798 for Fuel Ethanol and ASTM D4797 for Fuel Methanol.The ASTM D975-10a Specification for Diesel Fuel Oils defines petroleumdistillate grades, biodiesel, fuel oils, and sulfur content isincorporated by reference. The requirements specified for diesel fueloils are determined in accordance with the following test methods: flashpoint; cloud point; water and sediment; carbon residue; ash;distillation; viscosity; sulfur; copper corrosion; cetane number; cetaneindex; aromaticity; lubricity; and conductivity The ASTM D7467-08Specification for Diesel Fuel Oil, Biodiesel Blend is a newerspecification defining blends of fuel for on-and-off road vehicles.

In the examples below, combustion products of hydrocarbon fuel (definedas mol % concentrations) in an engine before the effluent emissions arealtered by the hydrocarbon fuel engine emissions systems are measured bycollecting vehicle emission gas samples in a stainless steel pipe beforethe catalytic converter. Vehicles were run 4 hours per fuel tank with anestimated gas collection temperature 300-400° C.

The exact method used and specified by the Gas Processors AssociationPublication, “Analysis for Natural Gas & Similar Gaseous Mixtures by GasChromatography” #2261 is incorporated by reference. A Perkin ElmerThermal Conductivity Detector (TCD) and Gas Chromatograph (GC) with a 15M GC capillary column was used for separation of effluent gascomponents.

The following examples are directed to a lithium nitrate fuel additive(the catalyst) comprising a 0.1 M solution LiNO₃ in isopropanol. The0.1M solution is prepared by adding 7.0 g of dry LiNO₃ to 1 L ofisopropanol. One ml of solution was then added to 7 kilograms fuel toobtain 1 microgram LiNO₃ in fuel. The fuel density is approximately 6.1to 6.3 lb/gal.

A total sample intake of 10-13 ppm LiNO₃, with a variation +/−1-2gallons fuel per test, was used for each vehicle example studied andreported.

In the data presented below baseline samples refer to fuel only with noadditive or catalyst. LiNO3 was added to fuel at 10-13 ppm/vehicle fueltank.

EXAMPLE 13

As shown, the use of Li in a gasoline-powered engine in accordance withthe method of this invention provides a combustion effluent gas having areduced carbon dioxide concentration.

Mol % Analysis Second Measurement #1 Dodge Truck Baseline C₆+ .071 CO₂5.340 N₂ 94.589 Btu Dry 3.6 Btu Sat 3.6 #1 Dodge Truck C₆+ .357 .246 CO₂.363 3.332 N₂ 99.280 96.422 Btu Dry 18.3 12.6 Btu Sat 18.0 12.4 #2 DodgeTruck Baseline C₆+ .063 CO₂ 5.423 N₂ 94.514 Btu Dry 3.2 Btu Sat 3.2 #2Dodge Truck C₆+ .286 .227 CO₂ 2.552 3.321 N2 97.162 96.452 Btu Dry 14.711.6 Btu Sat 14.4 11.4

EXAMPLE 14

As shown, the use of Li in a diesel-powered engine in accordance withthe method of this invention provides a combustion effluent gas having areduced carbon dioxide concentration and a reduced hexane concentration.

Mol % Analysis Second Measurement Diesel Tractor Baseline C₆+ .017 CO₂.308 N₂ 99.675 Btu Dry .9 Btu Sat .9 Diesel Tractor #1 C₆+ .007 .000 CO₂.110 1.242 (leak) N2 99.883 99.758 Btu Dry .4 .0 Btu Sat .4 .0 DieselTractor #2 C₆+ .000 CO₂ .075 N2 99.925 Btu Dry .0 Btu Sat .0

The increase in the C₆+ hexanes measurements indicate incompletecombustion of larger alkanes and other compounds which the TCD detectorverifies as a Btu measurement of that combustion product.

Data collected by this method indicates mole % analyses for Dodge trucksusing hydrocarbon based fuel to be approximately 5% CO₂ without thepresence of LiNO3 and reduced to approximately 3% or less CO₂ with thepresence of LiNO₃, and 07% C₆+ hexanes without the presence of LiNO₃ androughly increased by factors of 3-5 with the presence of LiNO₃.

As shown, the use of Li in a gasoline-powered engine in accordance withthe method of this invention provides a combustion effluent gas having areduced carbon dioxide concentration.

The results from Example 13 indicate the presence of LiNO₃ alters thecombustion of the gasoline hydrocarbon fuel in an engine. These resultsindicate an internal surface conditioned by combusting a hydrocarbonfuel containing a lithium salt provides a lithium conditioned surface,wherein the effluent gas has a lower concentration of carbon oxides thancombusting said fuel under similar conditions in an engine not having alithium conditioned surface. Thereafter, the lithium conditionedinternal surface in contact with combusting hydrocarbon fuel provides aneffluent gas with an effluent gas having a lower concentration of carbonoxides than combusting said hydrocarbon fuel under similar conditions inan engine not having a lithium conditioned surface.

Data collected by this method indicates mole % analyses for dieseltrucks using diesel hydrocarbon based fuel to be approximately 0.3% CO₂without the presence of LiNO₃ reduced to approximately 0.1% or less CO₂with the presence of LiNO₃, and approximately 0.017% C₆+ hexanes withoutthe presence of LiNO₃ and decreased with the presence of LiNO₃.

The results from Example #14 indicate the presence of LiNO₃ alters thecombustion of the diesel hydrocarbon fuel in a diesel engine. Theseresults indicate an internal surface conditioned by combusting ahydrocarbon fuel containing a lithium salt provides a lithiumconditioned surface, wherein the effluent gas has a lower mol %concentration of carbon oxides and lower mol % concentration of C₆+alkanes than combusting said diesel hydrocarbon fuel under similarconditions in an engine not having a lithium conditioned surface.Thereafter, the lithium conditioned internal surface in contact withcombusting diesel fuel provides an effluent gas wherein the effluent gashas a lower mol % concentration of carbon oxides and a lower mol %concentration of C₆+ alkanes than combusting said diesel fuel undersimilar conditions in an engine not having a lithium conditionedsurface.

Afterburner

A thermal oxidizer, also known as a thermal incinerator, is a devicethat can be used for air pollution control for combustion processes andin chemical plants for the decomposition of hazardous gases that requiremaximum destruction, or to treat exhaust gases generated in a processwhere combustion or emissions control is incomplete. These devices arealso referred to as afterburners or reheaters.

Many industries utilize these devices as fixed installations, which needto be supplemented at times of malfunction or overhaul of existingunits. In many cases the unique features of the technologies set forthabove, and claimed in applicant's prior patents to which priority isclaimed, can also be combined with movable equipment or vehicles to meetnew compliance requirements of regulatory bodies at a lesser expense,faster and with greater utility than by any other means. The key to thisadvantage is its ability to produce desired effects in much less processtime, at lower costs, and with restricted physical limitations asdemonstrated by applicant in testing programs showing a high level ofportability and efficiency of mobile unit design.

These devices can be adapted to receive upstream chemical processcontaminants, methane from landfills or sewage treatment plants, or coalmine ventilation air containing methane, CO, VOCs and CO₂ as well asexhaust streams from combustion sources having non-optimum emissionscontrol of off gases, such as CO, CO₂, NOx or SOx, and Hg, or any othergaseous contaminant or nuisance such as offensive odors from coatcombustion or refinery processing. Reduced emissions and increasedefficiencies also result when afterburners such as described herein areintegrated with emissions streams from engines, gas turbines, boilersand furnaces.

The improvements described herein below are primarily directed, but arenot limited, to methods for processing waste streams and emissions fromcombustion systems such as engines, turbines, boilers, and furnaces offixed design, particularly systems built and designed to operate usingspecific fuels, having specific operating characteristics and intendedto meet regulatory compliance requirements. Such systems often subjectedto changing operating requirements as a result of new laws andregulations, such as lower emissions standards, or are converted toaccommodate different fuels, such as biomass, natural gas or syntheticfuels, in an attempt to lower CO₂ and other emissions and to deal withchallenges like mercury reduction. There are many real-worlduncertainties that plant management must deal with not only comply withregulatory changes but also for competitive economic reasons involvinghuge costs often associated with new rules and operating requirements.The afterburner unit described herein provides a flexible andcost-effective answer to the wide range of operating challenges byproviding a portable reaction device readily adaptable to being added toexisting facilities to receive emissions from a broad range of sourcesand to provide a cleaner exit emission stream.

Also, among the problems faced by industry is that power plants arefixed systems by design and require monitoring and controlling vastquantities of potentially dangerous fuels that can cause disastrousexplosions and fires as well as dangerous high-pressure steam. Safecontrol of such systems requires highly qualified operators and complexcontrols because these systems are complex, dynamic and dangerous if notoperated properly. The addition of afterburners as described hereinavoids the complexity and danger of modifying front end control systemby providing the opportunity to separately treat the exhaust gasses tomeet changing emission standards.

Afterburners have been added to coal fired furnaces as well as otherchambers used to burn wood, coal or petroleum products and other organicmatter. In such instances the afterburner is typically used because theinitial burn in the primary combustion chamber is inefficient andresults in a significant level of numerous different pollutants, oftenreferred to as “products of incomplete combustion” or PICs, in theexhaust stream.

While there are numerous examples of after burners in the art, anexample of such an afterburner is disclosed in U.S. Pat. No. 9,803,857to Tiegs and the several prior patents cited therein, incorporatedherein by reference. The '857 patent is directed to an exhaust gasemissions reduction system comprising a reaction chamber (anafterburner) downstream of a primary combustion chamber, that reactionchamber also including an injector for adding an oxidizing agent. Thereaction chamber can be followed by a catalyst bed in fluidcommunication with the exhaust from the reaction chamber. The '857patent also discusses prior art thereto, for example U.S. Pat. No.3,468,634, U.S. Pat. No. 4,385,032, U.S. Pat. No. 4,476,852, U.S. Pat.No. 5,460,511, and U.S. Pat. No. 5,944,025 which include a catalyst bed(a catalytic converter) downstream from the primary combustion chamberfor reducing CO and volatile hydrocarbons but, according to Tiegs theyare not adequately effective unless an oxidizer is added. Further,particulate emissions are not adequately treated and they will depositon and foul the catalyst beds. On the other hand, the '857 patentdiscloses that heating exhaust streams to greater than 1500° F. (816°C.) without the addition of oxidizing agent largely obviates any needfor a catalyst bed as these temperatures are effective for rapidly andcompletely decomposing organic molecules in the exhaust streams andprevent buildup and fouling of surfaces. Contrary to the teachings ofTiegs, the afterburner systems described herein reduce or remove thesefouling factors and carbon buildup and provides heavier slag deposits sothat they are easier to remove during maintenance and clean up cycles.

The catalyst bed in the '857 patent comprises platinum oxide, palladiumoxide, or a combination of the two, located downstream from the reactionchamber, the PICs being reduced by adding the oxidizer into thecatalyst-free reaction chamber. According to Tiegs, an effective meansto achieve near-100% oxidation of PICs and organic particulates withoutheating exhaust streams to over 800° F. (427° C.) is to inject a strongoxidizing agent into the exhaust stream prior to heating in the reactionchamber channels. Temperatures significantly greater than 1500° F. (816°C.) can produce excessive NOx emissions, so lower temperatures may bedesirable. Many compounds are known which can be used to oxidize organiccompounds, but most have other undesirable characteristics. Chloride-and fluoride-based oxidizers can produce undesirable waste products, canbe dangerous to handle and can result in expensive repair andreplacement of exposed metal surfaces making use of such oxidizersundesirable. Oxidizers which are not completely consumed in reactionswith organics may themselves become unwanted pollutants. Cost of thechemicals and familiarity of the public with safety requirements arealso concerns. Tiegs has found that heat labile oxidizing agents arepreferred because any excess oxidizing agent will be destroyed by thehigh temperatures achieved inside the reaction chamber. Thus, manyoxidizing agents will function with such a system, but certain agentsare preferable. In particular, Tiegs finds the oxidizing agents ozone(O₃) and hydrogen peroxide (H₂O₂) added to the reaction chambermaintained at 600° F. (327° C.) to be especially effective foreliminating PICs from an exhaust steam that is maintained at greaterthan 800° F. (427° C.) before entering the reaction chamber.

Whether afterburners (reaction chambers) utilizing oxidizing agents, orcatalytic converters or elevated temperatures alone are used to destroyPICs, the intended purpose of those procedures is to substantiallyconvert carbonaceous materials in the exhaust stream leaving thecombustion chamber, generating large quantities of CO₂, which is nowconsidered to be an environment pollutant and allegedly a cause ofglobal warming.

The process described above and set forth in the above referenced parentpatents is directed to reduction of both CO and CO₂ in an exhaust stream100 exiting a combustion chamber buy adding a catalyst, preferablycomprising elemental lithium and/or boron, or compounds containinglithium and/or boron, preferably including a small quantity of a fuel asis necessary to assist in the combustion of the PICs in the exhaust 110fed to the afterburner 102. It has now been found that the quantities ofboth CO and CO₂ as well as other regulated pollutants in the exhauststream 100, 110 can be further reduced, without affecting the poweroutput and efficiency obtained from burning the fuel in the combustionchamber by passing the exhaust stream 100, or a portion 110 thereof,through an afterburner 102 and only feeding, from a fuel/catalyst mixingtank 104, a small amount of catalyst into the exhaust stream 110 in theafterburner 102, the exhaust 120 from the afterburner 102 having furtherreduced PICs, CO and CO₂ content.

The addition of the afterburner 102 described herein and shown in FIG.24 consistently provides a significantly improved burn efficiency andimprovements in the quality and content of emissions beyond prior designperformance levels in regard to CO₂ and other emissions.

As a further alternative, the hydrocarbon fuel feed entering thecombustion chamber can be burned in the most efficient manner known tothose skilled in the art without adding the catalyst to the combustionchamber. The exhaust 100 from that combustion, or a portion thereof 110,is then fed to the afterburner 102 along with a controlled quantity offuel/catalyst mixture. Alternatively, the afterburner 102 can bepre-seasoned by a prior lithium and/or boron feed thus reducing thequantity of catalyst that is added with the controlled quantity of fuel.Treating the fuel feeding the combustion chamber is then avoided becauseonly the exhaust gases 100, 110 are exposed in the after-burner 102 tothe presence of the lithium and/or boron catalyst to reduce the CO, CO₂and other undesirable emissions

A catalyst mixing and delivery system 104 is provided to deliver thecatalyst/fuel mixture to the afterburner 102 for treating exhaust gases110 passing therethrough. A small burner 108 ignites the fuel, such asdistillate oil, mixed with concentrated catalyst, the amount of eachprovided at a concentration and delivery volume for the exhaust stream110 flow and exhaust contents being treated. An oxygen containing stream(i.e., air) 116 can also be added to the afterburner 102 or the exhaust110 entering the afterburner. The exhaust gas 110 is then exposed to thecatalyst and reacted in a mixing chamber 112 in the afterburner 102, oran adjacent supplementary mixing and reaction chamber 114, reducing theCO and CO₂. An exhaust blower 120 or similar device can be attached tothe afterburner 102 to then inject the treated exhaust 118 exiting theafterburner 102 back into the original exhaust stream 100 or it can berecirculated via ducting 117 to the input exhaust stream 110, therecirculated flow being controlled by a damper 119, to continue toreduce emissions levels and CO₂ to provide a cleaner exhaust 122.

The quantity of exhaust gas treated by the afterburner 102 is regulatedbased on the affluent temperature, volume, and concentration of gasspecies in the exhaust 100, 110 to be controlled. As the composition offuels being burned may be variable, especially where the fuel is coal,operational adjustments of the afterburner 102 are monitored anddetermined by analysis of coal composition and the resulting CO₂ andother emissions in the exhaust steam 100, 110 reaching the afterburner102. The target properties of the cleaner exhaust 122 which aredetermined by specific environmental requirements encountered such astemperature, humidity and trace elements in the fuel with the operatingparameters of the processes described herein applied to produce requiredor optimum emission quality.

One skilled in the art will recognize, based on the teachings herein,that all of the exhaust 100 can be passed through the afterburner 102 orthe exhaust 100 can be divided into several side streams 110 which arethen treated in multiple afterburners 102.

Although there has been described hereinabove a catalyst conditionedengine, specifically a lithium catalyst conditioned engine, for reducedcarbon dioxide emissions in accordance with the present invention and anafterburner using a lithium and/or boron catalyst for reducing CO andCO₂ in an exhaust stream for the purpose of illustrating the manner inwhich the invention may be used to advantage, it should be appreciatedthat the invention is not limited thereto. That is, the presentinvention may suitably comprise, consist of, or consist essentially ofthe recited elements. Further, the invention illustratively disclosedherein suitably may be practiced in the absence of any element which isnot specifically disclosed herein. Accordingly, any and allmodifications, variations or equivalent arrangements which may occur tothose skilled in the art, should be considered to be within the scope ofthe present invention as defined in the appended claims.

I claim:
 1. In an improved process for reducing the ratio of CO₂/BTU ofenergy produced from the combustion of a carbon-based or hydrocarbonfuel in a combustion chamber with an oxygen containing gas whilemaintaining or increasing the efficiency of said combustion and reducingthe amount of pollutants produced in an exhaust stream exiting thecombustion chamber, wherein: a. following establishment of baselineoperating conditions for burning said fuel in an oxygen containing gasat an initial fuel/gas ratio to establish stable combustion with a baseline flame temperature and measuring the base line temperature, exhauststream composition and the energy output of the burning fuel during saidstable combustion, therein establishing a set of base line operatingparameters, b. adding an initial quantity of a catalyst comprisinglithium and/or boron or a lithium and/or boron compound to saidcombustion chamber while feeding the carbon-based or hydrocarbon fueland the oxygen containing gas at the initial fuel/gas ratio, to form acatalyst/fuel mixture, said catalyst/fuel mixture producing a differentstable flame temperature and an exhaust stream having a reduced CO₂ andCO composition when compared to the composition of the base lineoperating conditions exhaust stream, and c. once the components of theexhaust stream obtained during the combustion after the new stable flametemperature for the catalyst/fuel mixture is reached reducing thequantity of the catalyst delivered while maintaining the flame at athird temperature greater than the base line flame temperature, theimprovement comprising further reducing the CO₂ and CO in the combustionchamber exhaust buy providing an after-burner, said afterburnerreceiving the exhaust stream, the after-burner also configured toreceive and burn a fuel/lithium and/or boron catalyst mixture in saidexhaust stream.
 2. An improved process for reducing the ratio of CO₂/BTUof energy produced from the combustion of a carbon-based or hydrocarbonfuel in a combustion chamber while maintaining or increasing theefficiency of said combustion and reducing the amount of pollutants inan exhaust stream exiting the combustion chamber wherein: stableoperating conditions for burning said fuel in an oxygen containing gasis established at a preset fuel/gas ratio to generate a base line flametemperature, base line composition of the exhaust stream and the energyoutput of the burning fuel during said stable combustion, said base lineflame temperature and base line exhaust stream composition constitutinga baseline operating condition, and monitoring the baseline operatingcondition, including the CO₂ and CO concentrations in the exhauststream, the improvement comprising reducing the exhaust stream CO₂ andCO concentration by feeding the exhaust to an after-burner, saidafterburner configured to receive and burn a fuel/lithium and/or boroncatalyst mixture in the exhaust steam delivered thereto, wherein anoptimum feed rate and composition of the fuel/lithium and/or boroncatalyst mixture to reduce the CO₂ and CO concentration in said exhauststream is selected based on the base line operating conditions.
 3. Theprocess of claim 2 wherein an oxygen containing gas stream is also fedto the afterburner.